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An emulsion consists of two immiscible liquid phases, one of which is finely subdivided and uniformly dispersed as droplets in the other. This thermodynamically unstable system is stabilized by the presence of emulsifying agents. In pharmaceutical emulsions, one phase is usually water and the other oil, fat, or waxy substance. Systems in which oil is the dispersed, discontinuous, or internal phase and water is the continuous phase, dispersion medium, or external phase are termed oil-in-water emulsions. Conversely, water-in-oil emulsions are those in which the aqueous phase is dispersed in the oil. The ratio of the disperse phase volume to the total volume is known as the phase volume or phase volume ratio. Emulsions for external application are usually referred to as creams (semi-solids, lotions, or liniments (liquids). Emulsions typically contain globules ranging from 0.1 to 100 micrometers in diameter. Micro-emulsions, however, contain globules that have diameters of less than 0.1 micrometer.

Flocculation is the clumping together of globules into loose aggregates. The aggregates can often be dispersed by shaking as the interfacial films do not necessarily break . However, it is usual for flocculation to precede coalescence. Whereas flocculation is influenced by the electrical potential on the surface of the droplets, coalescence depends upon the structure of the interfacial film.

Creaming occurs in oil-in-water emulsions when the dispersed oil globules move upwards and accumulate at the top. In water-in-oil emulsions, sedimentation occurs owing to the accumulation of water droplets at the bottom. A creamed emulsion can usually be re-dispersed by agitation; however, creaming is undesirable because the closeness of the droplets in the cream favors breakdown of the oil/water interface and coalescence of the droplets. Since large droplets cream rapidly and coalesce more readily in the cream layer, the emulsion may eventually crack. Reducing the particle size of the dispersed globules, equalizing of the densities of the oil and water phases, and increasing the viscosity of the system are methods by which the rate of creaming can be reduced.

The viscosity of an emulsion may be increased by homogenization, by increasing the concentration of the disperse phase, by increasing the concentration of the emulsifying agent, by adding solid or semi-solid materials to the disperse phase, or by adding viscosity-increasing agents to oil-in-water emulsions.

Rupture of the interfacial film can lead to coalescence of the globules in the disperse phase . Coalescence may lead eventually to the complete and irreversible separation of the two phases; the term cracking is applied to such phase separation. Film breakdown can often arise from chemical incompatibility of the emulsifying agent with other constituents of the system; it may also be induced by exposure to increased or reduced temperatures or by the action of contaminant micro-organisms. Systems with a large phase volume and a closely packed disperse phase are prone to cracking.

Phase inversion
Phase inversion is the process by which the disperse phase of an emulsion becomes the continuous phase, and the continuous phase becomes the disperse phase. Following phase inversion, oil-in- water emulsion, for example, becomes a water-in-oil emulsion. Phase inversion may occur in a number of ways. If the amount of the disperse phase is increased until it approaches or exceeds the theoretical maximum of 74% of the total volume, the emulsion may invert; alternatively, the emulsion may break down completely. Temperature changes, or the addition of a material that changes the solubility of the emulsifying agent, may also cause phase inversion. Phase inversion occurs at the phase inversion temperature. Inversion may also occur in systems manufactured using dirty equipment or prepared using incorrect mixing procedures.

FORMULATION Antioxidants Inhibition of the rancidity and spoilage that can result from oxidation can be achieved by the inclusion of antioxidants such as the Alkyl gallates, butylated hydroxyanisole, butylated hydroxytoluene, and tocopherols Preservation The polymorphic nature of emulsions presents special problems in preservation due to partitioning of the preservative between the oily and the aqueous phases. To protect the product it is necessary to have an effective bactericidal and fungicidal concentration of preservative in the aqueous phase; however, in order to achieve this, the total

concentration of preservative required may be clinically unacceptable if the preservative has a high partition coeflicient between the particular oil and water. Examples of antimicrobial agents used to preserve emulsion systems include chlorocresol, chloroform, hydroxybenzoate esters, organic acids such as sorbic acid and benzoic acid, organic mercurials such as phenylmercuric acetate and phenylmercuric nitrate, phenoxyethanol, quaternary ammonium compounds such as cetrimide, and sodium benzoate. The presence of nonionic emulsifying agents such as polysorbates or compounds with polyoxyethylene groups can inhibit or inactivate phenolic preservatives, while hydroxybenzoate esters can be partially inactivated by binding with polysorbates, povidone, certain macrogols, methylcellulose, and gelatin. Complexation of methylcellulose with hydroxybenzoates has also been reported.

Emulsifying agent Emulsifying agents prevent coalescence of the dispersed globules in emulsified systems by forming barriers at the interface; they may also facilitate the initial dispersion of globules by reducing interfacial tension. The stability of a prepared emulsion is primarily determined by the strength and nature of the interfacial film formed. It is important to use only the minimum concentration of the chosen emulsifying agent as any excess may result in the formation of foam. The ideal emulsifying agent for pharmaceutical purposes should be stable, inert, and free from toxic and irritant properties, it should be odourless, tasteless, colourless, and low concentrations should produce stable emulsions of the desired type. Surfactants can be divided into four groups: anionic, cationic, nonionic, and ampholytic. 1. Anionic Surfactants. stable over the pH range 7 to 8 Soaps formed from long-chain (C12 to C18) fatty acids, sulphated alcohols, and sulphonates comprise many of the anionic emulsifying agents in common use. On dissociation, the long-chain anion imparts surface activity, while the cation is inactive. Examples of Anionic Surfactants Fatty acids- Stearic acids Alkali metal and ammonium soaps Soaps of divalent and trivalent metals Amine soaps Alkyl sulphates Alkyl Phosphates Alkyl Sulphonates Carbomer

2. Cationic Surfactants

stable over the pH range 3 to 7

Cationic surfactants dissociate to yield a surface-active cation and an inactive anion (see also the Disinfectants and Antiseptics chapter). Like the anionic surfactants, they require to be ionised to be effective. Quaternary ammonium compounds, such as cetrimide, benzalkonium chloride, and domiphen bromide, are the most important cationic surfactants. 3. Non-ionic surfactants The nonionic surfactants constitute the largest group of surface active compounds and are used to produce oil-in-water and water-in-oil emulsions for both external and internal administration. The advantages of nonionic derivatives include their resistance to the effects of electrolytes, their compatibility with other surfactants, and their stability, in general, between pH 4 and 9. Emulsions made with nonionic surfactants are usually less irritant than those made with ionic derivatives. A disadvantage of nonionic surfactants is their tendency, when present in excess, to bind or to inactivate preservatives having phenolic or carboxylic acid groups.

Examples of non-ionic Surfactants

Esters of polyhydric alcohols Macrogol esters poloxyl 8 stearate Macrogol ethers e.g. cetomacrogol 1000 Sorbitan esters sorbitan monolaurate, sorbitan monopalmitate Polysorbates polysorbate 20 Long chains alcohols e.g cetostearyl alcohol, cetyl alcohol, stearyl alcohol PoloxamersPolyvinyl alcohols

4. Ampholytic surfactants Not usually widely used as emulsifying agents; their chief application are as bactericidal detergents.

Emulsifying agents derieved from natural products 1. Polysaccharides derieved from vegetable sources Tragacanth Acacia Agar (a poor emulsifying agent but produces viscous mucilage or gels) Starch (also a poor emulsifying agent but acts as a stabilizer by forming a continuous phase of high viscosity). Pectin Carrageenan (from seaweed) - more effective viscosity- increasing agent than primary emulsifying agents. Other emulsifying agent derived from seaweeds is sodium alginate Carmellose sodium, hydroxypropyl cellulose, methylcellulose are common emulsifying and viscosity increasing agents. 2. Steroidal materials- derieved from animals Wool fat wool alcohol Beeswax Cholesterol Bile salt e.g sodium glycocholate and sodium taurocholate Mineral oil and lanolin alcohol 3. Glycerides monoglycerides, diglycerides 4. Phospholipids lecithin presentin egg yolk and soya bean oil lecithin yields o/w emulsion 5. Protein gelatin, casein 6. Saponins